CN113444523A - Preparation of matrix-free long afterglow carbon dots, and afterglow type regulation method and application - Google Patents
Preparation of matrix-free long afterglow carbon dots, and afterglow type regulation method and application Download PDFInfo
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- CN113444523A CN113444523A CN202110820098.5A CN202110820098A CN113444523A CN 113444523 A CN113444523 A CN 113444523A CN 202110820098 A CN202110820098 A CN 202110820098A CN 113444523 A CN113444523 A CN 113444523A
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/65—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing carbon
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Abstract
The invention discloses a preparation method of matrix-free long afterglow Carbon Dots (CDs) and an afterglow type regulation method and application. The invention prepares six kinds of polymer matrix-free long afterglow CDs by a one-step hydrothermal method. Due to the structure of this polymer, a rigid host is provided for CDs, thereby protecting triplet excitons of CDs from quenching by oxygen and moisture in the environment. By regulating and controlling the rigid structure of the prepared CDs, the regulation and control between room-temperature phosphorescence and delayed fluorescence can be effectively realized. The CDs with long afterglow emission show potential in the aspects of information anti-counterfeiting, encryption and the like.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a long afterglow carbon dot and application thereof.
Background
Counterfeit goods such as currency, fuel, microelectronics, and clothing are spreading in the current market, causing economic losses to customers and copyright owners. At present, various anti-counterfeiting and information encryption technologies have been developed and widely used in the fields of economy, military affairs and our personal daily lives. Among the existing anti-counterfeiting and information encryption technologies, the fluorescent marking technology has received wide attention due to its convenient identification process. However, similar emission characteristics can be obtained by using certain alternatives or simply mixing different fluorescent materials, thus exhibiting poor anti-counterfeiting and information encryption properties. And the after-glowing material can effectively avoid the above disadvantages. Compared with the traditional afterglow material, the Carbon Dot (CDs) based afterglow material has higher stability, low toxicity and long afterglow time, so that the Carbon Dot (CDs) based afterglow material has greater advantages in the fields of information anti-counterfeiting and encryption. However, currently, most CDs-based afterglow materials require the incorporation of CDs into a rigid matrix in order to achieve long afterglow emission. However, the preparation process of these methods is generally complicated, has certain environmental toxicity and requires a lot of time to screen suitable substrates, which severely limits the application of the long-afterglow CDs in various fields. Furthermore, regulation of the type of afterglow associated with CDs is currently difficult to achieve. Therefore, the preparation and development of a substrate-free long afterglow carbon dot and the control of the afterglow type thereof are crucial.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of a substrate-free long afterglow carbon dot and an afterglow type regulation method and application.
One of the technical schemes adopted by the invention for solving the technical problems is as follows:
a method for preparing a substrate-free long afterglow carbon dot and regulating the afterglow type comprises the following steps: carrying out hydrothermal reaction on a benzoic acid derivative and ethylenediamine at 140-220 ℃ for 6-16 hours, cooling to room temperature to obtain a CDs solution, removing impurities, and drying to obtain solid long afterglow CDs powder; the formula ratio of the benzoic acid derivative to the ethylenediamine is 0.1-2 g: 100 to 2000 μ L.
Further, in the above regulation and control method, the afterglow type can be regulated and controlled by changing different benzoic acid derivatives. For example, the benzoic acid derivative includes at least one of phthalic acid, isophthalic acid, terephthalic acid, hemimellitic acid, trimesic acid, or trimellitic acid. The afterglow type of the CDs prepared from the isophthalic acid, the terephthalic acid and the trimesic acid is room-temperature phosphorescence, and the afterglow type of the CDs prepared from the phthalic acid, the hemimellitic acid and the trimellitic acid belongs to delayed fluorescence.
Preferably, the formula ratio of the benzoic acid derivative to the ethylenediamine is 0.8-1.2 g: 450-550 mu L; further, in the hydrothermal reaction, the formula ratio of the benzoic acid derivative, the ethylenediamine and the water is 0.8-1.2 g: 450-550 μ L: 9-11 mL.
Preferably, the hydrothermal reaction temperature is 195-205 ℃, and the reaction time is 11-13 hours.
Further, the hydrothermal reaction is carried out in an autoclave lined with polytetrafluoroethylene.
Further, the reaction is carried out in an oven.
Further, the method for removing impurities is to use a 0.22 μm filter membrane for treatment to remove large particles.
Further, after cooling to room temperature, the product is vacuum freeze-dried into powder to obtain the long afterglow CDs powder.
The second technical scheme adopted by the invention for solving the technical problems is as follows:
a substrate-free long afterglow carbon dot comprises the solid long afterglow CDs prepared by the method.
The third technical scheme adopted by the invention for solving the technical problems is as follows:
an application of a substrate-free long afterglow carbon dot.
Further, the application comprises information anti-counterfeiting and encryption.
The substrate-free long afterglow CDs are prepared by a one-step hydrothermal method and are used for information anti-counterfeiting and encryption. The prepared CDs have polymer characteristics, and due to the structure of the polymer, triplet excitons of the CDs are protected from being quenched by the external environment, so that long afterglow emission is realized. The regulation and control of the delayed fluorescence and the room temperature phosphorescence are realized by adjusting the position of the carboxyl substituent on the benzene ring of the raw material. The invention effectively solves the problem that the long afterglow emission and the long afterglow mode are difficult to regulate and control only by doping CDs into a rigid matrix at present. And the prepared long afterglow CDs have potential in the aspects of information anti-counterfeiting and encryption.
The equipment, reagents, processes, parameters and the like related to the invention are conventional equipment, reagents, processes, parameters and the like except for special description, and no embodiment is needed.
All ranges recited herein include all point values within the range.
In the invention, the room temperature, namely the normal environment temperature, can be 10-30 ℃.
Compared with the background technology, the technical scheme has the following advantages:
1. the raw materials of the invention are cheap and easy to obtain, and are environment-friendly.
2. The invention effectively overcomes the defect that long-afterglow emission can be realized only by doping CDs into a rigid matrix at present.
3. According to the invention, the positions of the carboxylic acid substituent groups on the benzene ring of the raw material are regulated, so that the regulation of delayed fluorescence and room temperature phosphorescence can be realized.
4. CDs prepared by the method have long afterglow life.
5. The CDs prepared by the method can be used for information anti-counterfeiting and encryption.
Drawings
FIG. 1 is a TEM image of six CDs prepared by an example of the present invention.
FIG. 2 is a digital photograph of six CDs before and after turning off 365nm light.
FIG. 3 is a graph showing fluorescence and afterglow spectra of six CDs.
FIG. 4 shows CDs powder prepared by the embodiment of the invention for information anti-counterfeiting and encryption.
Detailed Description
The invention is further illustrated by the following figures and examples.
Example 1:
1) 1.0g of the benzoic acid derivative and 500. mu.L of the ethylenediamine solution were weighed into 10mL of ultrapure water, and then the above solution was transferred to a 50mL autoclave lined with polytetrafluoroethylene, and after heating at 200 ℃ for 12 hours, cooled to room temperature to obtain a CDs solution, which was stored in a refrigerator at 4 ℃.
2) Treating the CDs solution obtained in the step 1) by using a 0.22-micron filter membrane to remove large particles;
3) and (3) carrying out vacuum freeze drying on the CDs solution obtained in the step 2) to obtain solid long-afterglow CDs powder, and storing the solid long-afterglow CDs powder in a dryer.
In the step 1), the benzoic acid derivatives are respectively selected from phthalic acid (the prepared product is designated as Pht-CDs), isophthalic acid (the prepared product is designated as Iso-CDs), terephthalic acid (the prepared product is designated as Ter-CDs), hemimellitic acid (the prepared product is designated as Hem-CDs), trimesic acid (the prepared product is designated as Tri-CDs), and trimellitic acid (the prepared product is designated as Ben-CDs), and the preparation of the CDs is respectively carried out.
Example 2:
1) 1.0g of the benzoic acid derivative and 500. mu.L of the ethylenediamine solution were weighed into 10mL of ultrapure water, and then the above solution was transferred to a 50mL autoclave lined with polytetrafluoroethylene, and after heating at 200 ℃ for 12 hours, cooled to room temperature to obtain a CDs solution, which was stored in a refrigerator at 4 ℃.
2) Treating the CDs solution obtained in the step 1) by using a 0.22-micron filter membrane to remove large particles;
3) and (3) carrying out vacuum freeze drying on the CDs solution obtained in the step 2) to obtain solid long-afterglow CDs powder, and storing the solid long-afterglow CDs powder in a dryer.
4) The CDs powder prepared in the step 3) is used for information anti-counterfeiting and encryption.
In the step 1), the benzoic acid derivatives are respectively selected from phthalic acid, isophthalic acid, terephthalic acid, hemimellitic acid, trimesic acid and trimellitic acid, and the CDs are respectively prepared.
In FIG. 1, there are shown TEM images of six CDs prepared by example, and it can be seen that the six CDs all show good dispersibility, uniform size and have a spheroidal structure.
FIG. 2 is a digital photograph of six CDs before and after turning off the 365nm UV lamp, from which it can be seen that the produced CDs can be observed with the light source removed, with persistence lasting for several seconds; the afterglow of CDs prepared from the intermediate phthalic acid and the trimesic acid has longer duration.
FIG. 3 is the fluorescence and afterglow emission spectra of six CDs, from which it can be seen that the afterglow emission wavelengths of Iso-CDs, Ter-CDs, Tri-CDs, Pht-CDs, Hem-CDs and Ben-CDs powders at room temperature are 505nm, 520nm, 495nm, 497nm, 515nm and 513nm, respectively. Wherein the afterglow type of the Iso-CDs, Ter-CDs and Tri-CDs powders is room temperature phosphorescence, and the afterglow type of the Pht-CDs, Hem-CDs and Ben-CDs powders is delayed fluorescence.
Fig. 4 is a digital photograph of CDs powder used for information anti-counterfeiting and encryption in embodiment 2 of the present invention, wherein a colorful butterfly and "8888" can be observed under 365nm uv light, and once the excitation light source is turned off, the butterfly pattern can be seen to alternate yellow and green and the number can be seen to be "2021".
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims and their equivalents.
Claims (10)
1. A method for preparing a substrate-free long afterglow carbon dot and regulating and controlling the afterglow type is characterized in that: the method comprises the following steps: carrying out hydrothermal reaction on a benzoic acid derivative and ethylenediamine at 140-220 ℃ for 6-16 hours, cooling to room temperature to obtain CDs solution, and drying to obtain solid long-afterglow CDs; the formula ratio of the benzoic acid derivative to the ethylenediamine is 0.1-2 g: 100 to 2000 μ L.
2. The method of claim 1, wherein: the control of the afterglow type is realized by changing different benzoic acid derivatives.
3. The method of claim 1, wherein: the benzoic acid derivative comprises at least one of phthalic acid, isophthalic acid, terephthalic acid, hemimellitic acid, trimesic acid or trimellitic acid.
4. The method of claim 1, wherein: the formula ratio of the benzoic acid derivative to the ethylenediamine is 0.8-1.2 g: 450 to 550 μ L.
5. The method of claim 1, wherein: the hydrothermal reaction temperature is 195-205 ℃, and the reaction time is 11-13 hours.
6. The method of claim 1, wherein: the hydrothermal reaction is carried out in an autoclave lined with polytetrafluoroethylene; the drying is vacuum freeze drying.
7. A substrate-free long afterglow carbon dot is characterized in that: the substrate-free long afterglow carbon dots comprise solid state long afterglow CDs prepared according to the method of any one of claims 1 to 6.
8. Use of the substrate-free long afterglow carbon dots of claim 7.
9. Use according to claim 8, characterized in that: the application includes information security.
10. Use according to claim 8, characterized in that: the application includes encryption.
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|---|---|---|---|---|
| CN112521931A (en) * | 2020-12-15 | 2021-03-19 | 四川大学 | Room temperature phosphorescence test strip based on carbon dots and preparation method and application thereof |
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